Pyridazone derivatives and their use as herbicides



. chlorine atoms, bromine View? e 9.

3,341,317 PYRIDAZONE DERIVATIVES AND THEIR USE AS HERBICIDES Franz Reicheneder and Franz Winter, Ludwigshafen (Rhine), and Adolf Fischer, Mutterstadt, Pfalz, Germany, and Karl Dury, deceased, late of Kirchheimbolanden, Pfalz, Germany, by said Franz Winter, representative of the heirs, assignors to Badische Anilin- & Soda Fahrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany N Drawing. Filed Aug. 3, 1966, Ser. No. 570,091 Claims priority, application Germany, Aug. 17, 1965,

B 83,287; Aug. 25, 1965, B 83,429 Claims. (Cl. 71-92) The present invention relates to new pyridazone derivatives. It relates particularly to pyridazone derivatives derived from carbamic acid and having a good herbicidal action.

It is an object of this invention to provide new and valuab' e pyridazone derivatives. Another object of the invention is to provide a process for controlling unwanted vegetation, particularly in crop plants without damage to the crop plants.

It is known that 1 phenyl 4 amino S-chloropyridazone-6 (referred to hereinafter as (A) and 2-chloro-4,6- bis-ethylamino)-s-triazine (referred to hereinafter as (B) may he used as heribicida'l active ingredients. Their effect is however unsatistactor We have found that herbicidal compositions which contain a pyridazone derivative having the formula:

denotes the radical -COXR in which X denotes =0 or Q and R denotes the radical in which R denotes an ethylene radical, a propylene radical or a butylene radical and R R and R have the above meanings, or R may also have the following meanings: an alkyl radical having having one to eighteen carbon atoms which may bear as substituents hydroxyl groups, methoxyl groups, ethoxyl groups, carboxyl groups,

atoms, thiocyano groups or dialkylamino groups having one to four carbon atoms in each alkyl radical, or an alkenyl radical having three or 2,341,211 Patented Sept. 12, 1967 four carbon atoms which may :bear chlorine atoms as substituents, or an carbon atoms, or a phenyl radical which may bear as substituents chlorine atoms, bromine atoms, hydroxyl or alkyl groups, or a cyclohexyl radical, a cyclooctyl radical, the benzyl radical, acetonimino radical, dichlorocrotonolactone radical, tetrachlorotetrahydrofuran radical or the bicycloheptenylmethylene radical, have good herbicidal action.

The new active ingredients may be prepared lay reaction of the appropriate 4-aminopyridazones with phosgene or thionyl chloride, reaction of 4 isocyanatopyridazones or the corresponding carbamyl chlorides with the appropriate alcohols, glycols, phenols, thioalcohols or thiophenols.

The following methods of preparing the new active ingredients are given by way of example.

Production of I-phenyl-4-isocyanato 5-brom0- pyridazone-(6) Production of N-(1-phenyl-5-chloropyridaz0n-6) yl-carbamoyl-fl-hydroxyethyl ester 25 parts (by Weight of l-phenyl-4-isocyanato-5-chloropyridazone-(fi) dissolved in 100 parts of benzene is mixed with 8 parts of glycol and the mixture boiled for 10 minutes under reflux. After the reaction solution has been reduced and cooled the crystallized N-( l-phenyl-S-chloropyridazon-6) 4 yl carbamoyl-B-hydroxyethyl ester is suction filtered. 29 aparts of the ester recrystallized from acetic acid melt at 168 to 170 C.

Production 0 1-phenyl-4-sulfinylamino-5- ch loropyridazone- (6 volume. After cooling the resulting solid substance is suction filtered, washed with water and recrystallized from acetonitrile. 20 parts of l-phenyl-4-sulfinylamino-5-chloropyridazone-(6) having a melting point of 240 to 241 C. is obtained.

The following active substances are given as examples: R3

g o p R1 R2 R3 R4 R5 X M.P., 0.

01 =s=0 =0 240 to 241;

- 01 =o=0 =0=0 s to 154;

@ Br =o=o =c=0 144 to 146.

01 =0 c -0 121 to 123;

-- 01 H -0 0x145 CHa o 142 to 143.

Q 01 H -0 0x125 07H; 0 to 111.

- 01 H -o 0x115 CnH1-CHOH o 168 to 170.

Q 01 H -0 0x115 CHz CHaOH7H5 0 67 to 71.-

Q 4 01 H c 0x125 41111-02011 0 I 164150 166.

01 H -0 0x111 --C8H11 o 53 to 54 01 H -0 0x115 -1C0H1n 0 as to 62.

-- 01 H --0 0x115 -018H11 0 661:0 e9.

/CECH Q 01 H -0 0x111 -CCH1-CH1 0 14s to 145.

-@ 01 H -0 OXRs 0 12010 122. 01 H --0 0x111 @OH 0 19s to 19s. 01 H 410x c1 o to 170.

- 01 H -ooxm -01 o 172 to 17s.

01 H -o 0x115 oH1- L 0 14s to 149.

01 01 c1 o1 HQ 01 H --0 0x111 o 147 to 150.

01 c1 01 H -0 0x111 zf 0 157 to 160.

\ C=OX a R1 R! R4 R x M.P., 0.-

/CH3 or H -o OXRs -N=o 148t0149.

0 Br H -o 0x115 -0H5 0 1061:0107.

@ 01 H C0XR5 -CHa 0 104 to s.

01 H -o 0x111 Q s 1431:0145.

fi 01 H -0 0x115 o1 s 159 to 160. g or H --0 0X12, Br s 1651:0168.

01 H -o OXRs -oH=.o=o 01 s as to s9 c1 or f 01 H COXR5 CHOH:COOH s 165.

CzHs o1 11 ooxa CH:CHa- .1101 s 174m 117.

CzHr,

V 7 f H 01 H --0 0x125 -CH4-CHr0-C-III s 194 to 199. t i 1-m o=o N.

1 Dtacomposltlon:

The herbicides according to this invention may be prepared *by conventional methods by mixing the active ingredients with solid or liquid carriers, for example water, hydrocarbons, clay, fertilizers, -borax or diatomaceous earth. It is also possible to add wetting agents, dispersing agents, adhesives'or other biologically active ingredients.

The following examples illustrate the use of the herbicides according to this invention and their advantages over prior art herbicides.

EXAMPLE 1 Seeds of Indian corn (Zea mays), barleyv (Hordeum vulgare), wheat (Triticum vu'lgare), cotton (Gossypium sp.), peas (Pisum sativum), beet (Beta vulgaris), wild mustard (Sinapis arvensz's), white goosefoot (Chenopodiam album), chickweed (Stellaria media), gallant soldier (Galinsoga parviflora) and annual meadow grass (Poa annua) are sown in plastics pots having a diameter of 8 cm. in a greenhouse and on the same day treated with 1- phenyl 4 sulfinylamino 5 chloropyridazone 6 (I), 1 phenyl 4 isocyanato 5 bromopyridazone 6 (l1) and, for comparison, with A. The rate of application is 2 kg. per hectare of active ingredient dispersed in an amount 7, of water equivalent to 500 liters per hectare. The results of the experiment may be seen in the following table:

Active ingredient Crop plants:

Indian com.-

Barley" Wheat Cotto Peas.

White goosefo 90 80. Chickweed 1 Gallant soldier 80 to 90 80 to 90 70 to 80. Annual meadow grass 70 70 to 80.... 60 to 70.

=no damage; 100:total destruction.

In the above Example 1 and in the following Examples 2, 3 and 4, the following compounds have the same biological action as compounds I and II:

The plants vulgare), wheat (Triticum vulgare), sorrel (Rumex sp.), wild mustard (Sinapis arvensis), white goosefoot (Chenopodium album), chickweed (Stellaria media) and gallant soldier (Galinsoga parviflora) are treated at a growth height of 5 to 16 cm. with I, II and, for comparison, with A. The rate of application is 2 kg. per hectare of active ingredient, dispersed in an amount of Water equivalent to 500 liters per hectare. The

Indian corn (Zea mays), barley (Hordeum beet (Beta vulgaris),

results of the experiment are given in the following table:

Active ingredient I II A 0:110 damage; 100=total destruction.

8 EXAMPLE 3 An agricultural cultivated area is sown with wild mustard (Sinapis arvensis), white goosefoot (Chenopodiiumalbum), chickweed (Stellaria media), gallant soldier (Galinsoga parviflora), sorrel (Rumex sp.), annual meadow grass (Poa unnua) and slender foxtail (Alopecurus myosuroides) and treated on the day of sowing with I, II and B. The rate of application is 5 kg. per hectare of active ingredient disprsed in an amount of water equivalent to 500 liters per hectare. After the plants have emerged it is evident that I and II have a stronger initial herbicidal effect. Four weeks later almost all the plants have completely withered.

EXAMPLE 4 I, II and B are sprayed onto an agricultural cultivated area which is overgrown with wild mustard (Sinapis arvensis), white goosefoot (Cheno podiurm album), chickweed (Stellaria media), gallant soldier (Galinsoga parviflora), sorrel (Rumex sp.), annual meadow grass (P011 annua) and slender foxtail (Alopecurus myosuroides) at a growth height of the plants of 3 to 9 cm. The rate of application is 5 kg. per hectare of active ingredient dispersed in an amount of water equivalent to 500 liters per hectare. A few days later it is evident that compounds I and II have a stronger initial herbicidal action than B. Three weeks later almost all the plants have withered. EXAMPLE 5 Seeds of beet (Beta vulgaris), Indian corn (Zea mwys), white goosefoot (Chenopodium album), arnaranth pigweed (Amaranthus retroflexus), chickweed (Stellaria media), small nettle (Urtica uren's), camomile (Matricaria chamomilla), wild mustard (Sinapis arvensis) and annual meadow grass (Poa wnnua) are sown in plastics pots in a greenhouse and are treated on the same day with N (l phenyl 5 chloropridazon 6) 4 yl carbamoylfi-hydroxyethyl ester (HI) and, for comparison, with A. The rate of application is 2 kg. of active ingredient per hectare dispersed in an amount of water equivalent to 500 liters per hectare.

The results of the experiment four weeks after the treatment may be seen from the following table:

Compounds Active ingredient 0=n0 damage; :total destruction.

The following compounds have the same biological action as compound III in the above Example 5 and in the following Examples 6, 7 and 8.

ethyl N-(1-phenyl-5-chloropyridazon-6)-4-y1 carbamate ethyl N-(1-phenyl-5-bromopyridazon-6)-4-yl carbamate phenyl N-(1-pheny1-5 chloropyridazon-o)-4-yl carbamate phenyl N-(1-phenyl-5-bromopyridazon-6)-4-yl carbamate p-hydroxyphenyl N-(1-pheny1-5chloropyridazon-6)- 4-yl carbamate p-hydroxyphenyl N-(1-phenyl-5bromopyridazon 6)- 4-y1 carbamate phenylthiol N-(1-phenyl-5-chloropyridazon-6)-4-yl carbamate phenylthiol N-(1-phenyl-5-bromopyridazon-6)-4-yl carbamate tion than active ingredient B. Three weeks later almost all the plants are completely dead.

We claim: 1. A pyridazone derivative of the formula N o N in which R is a member selected from the group consisting of phenyl, fluoro-substituted phenyl, chloro-substituted phenyl, lower alkyl-substituted phenyl, cyclohexyl, cyclooctyl and cyclohexenyl, R is a member selected from the group consisting of chlorine, bromine, methoxyland thiomethyl, R and R together form 07 0 or -=S O, or R is a member selected from the group consisting of hydrogen and alkyl of one to four carbon atoms and R denotes -COXR in which X denotes =0 or :S and R is a member selected from the group consisting of R -0OON-R R O \OH in which R denotes ethylene, propylene or butylene and R R and R have the above meanings, alkyl of one to eighteen carbon atoms, a hydroXyl-substituted alkyl of 1 to 18 carbon atoms, methoxyl-substituted alkyl of 1 to 18 carbon atoms, ethoXyl-substituted alkyl of 1 to 18 carbon atoms, carboxyl-substituted alkyl of 1 to 18 carbon atoms, chloro-substituted alkyl of l to 18 carbon atoms, bromo-substituted alkyl of 1 to 18 carbon atoms, thiocyano-substituted alkyl of 1 to 18 carbon atoms, dialkylamino-substituted alkyl of 1 to 18 carbon atoms, each of said alkyls containing 1 to 4 carbon atoms, a1- kenyl of three or four carbon atoms, chloro-substituted alkenyl of 3 to 4 carbon atoms, alkinyl of three to six carbon atoms, phenyl chloro-substituted phenyl, bromosubstituted phenyl, hydroxyl-substituted phenyl, lower alkyl-substituted phenyl, cyclohexyl, cyclooctyl and benzyl radical.

2. 1-phenyl-4-sulfinylamino-5-chloropyridazone-6.

3. l-phenyl-4-isocyanato-5-bromopyridazone-6.

4. B-hydroxyethyl N-(1-phenyl-5-chloropyridazone-6)- 4-yl carbamate.

5. A method of controlling unwanted plants wherein the plants or the soil in which the plants are growing or are to grow are treated with a phytotoxis quantity of the pyridazone derivative as claimed in claim 1.

No references cited.

NICHOLAS S. RIZZO, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,341 ,317 September 12 1967 Franz Reicheneder et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 5 and 6 in the table last column, last line for "194 to 199" read 194 to 195 column 8, line 9, for "disprsed" read dispersed line 37, for "chloropridazon" read chloropyridazon column 11,

lines 8 to 17, for that portion of the formula reading I l C C=O read N N column 12, line 26, for "phytotoxis" read phytotoxic Signed and sealed this 22nd day of April 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A PYRIDAZONE DERIVATIVE OF THE FORMULA
 5. A METHOD OF CONTROLLING UNWANTED PLANTS WHEREIN THE PLANTS OR THE SOIL IN WHICH THE PLANTS ARE GROWING OR ARE TO GROW ARE TREATED WITH A PHYTOTOXIS QUANTITY OF THE PYRIDAZONE DERIVATIVE AS CLAIMED IN CLAIM
 1. 